JPS60180197A - Method for manufacturing multilayer printed wiring board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for manufacturing a multilayer printed wiring board, in particular,
As a material for forming the glabellar insulating film of multilayer printed wiring boards, it is made of a new highly sensitive aromatic polyamide containing photosensitive groups in the polymer chain, and has excellent heat resistance, mechanical properties, and electrical properties. The present invention relates to a method for manufacturing a multilayer printed wiring board using a photosensitive resin composition having high resolution and containing an organic solvent-soluble polyamide as a photosensitive material.

Traditionally, the elements and parts mounted on printed wiring boards have mainly been individual parts, including active and passive elements, but as technology advances, the future trend is toward high-density mounting of ICs and LSIs. it is conceivable that. Accordingly, printed wiring boards tend to be more complex and densely packaged.

However, it is completely impossible to cope with the increase in the density of printed wiring boards using conventional printed wiring technology, and new high-density fine line circuit formation technology and multilayer technology are required.

That is, for example, in printed wiring boards, in order to increase the number of wires that can be accommodated, multilayer technology using the Menki through-hole method has been widely applied. The disadvantage is that the wiring area is limited.

That is, when a printed wiring board is multilayered using the above-mentioned conventional technique, there is a drawback that as the number of layers increases, the number of through holes for connecting between the eyebrows increases, and conversely, the wiring area in a plane decreases. Therefore, with conventional technology, increasing the number of layers to 10 or more and reducing the diameter of wires 11 and through holes is reaching its limits both in terms of materials and precision, and new wiring technology is needed to increase the number of layers in printed wiring boards. is requested.

Therefore, as the above-mentioned new wiring technology, there is a method that applies photofabrication to the formation of pie holes, that is,
After forming a first layer wiring pattern on an insulating substrate and forming a photopolymer film on the wiring pattern, the photopolymer film is exposed to light to be photocured and developed to form a pie hole in a predetermined position. The photocured film thus formed is formed, and then a second photocured film of the photopolymer is used as an insulating film between the eyebrows, and a second film is formed on the insulating film between the eyebrows and in the pie hole portion.
A method of manufacturing a multilayer printed wiring board may be considered, in which a multilayer wiring pattern is formed by forming a wiring pattern for each layer, and then sequentially repeating the steps from the photopolymer film forming step described above to form a multilayer wiring pattern.

However, in order to manufacture a multilayer printed wiring board by the above method, the photopolymer described above must not only have various suitability as a photosensitive material but also have properties such as the ability to form an insulating film between the eyebrows. However, conventional photopolymers do not necessarily have such properties;
It was difficult to apply this method to the above-mentioned method for manufacturing a multilayer printed wiring board.

The present inventors have conducted various studies on a method for manufacturing a multilayer printed wiring board by applying photofabrication and a photopolymer that enables implementation of the manufacturing method.
The present invention was achieved by discovering that a multilayer printed wiring board having sufficient industrial value can be produced by using a specific aromatic polyamide containing a photosensitive group as a photopolymer.

That is, in the present invention, a first layer wiring pattern is formed on an insulating substrate, a photopolymer film is formed on the wiring pattern, and then the photopolymer film is photocured by exposure and developed. Then, a photocured film with pie holes formed therein is formed at a predetermined position, and then, using the photocured film of the photopolymer as an insulating film between the eyebrows, a second layer wiring pattern is formed on the insulating film between the eyebrows and in the part of the pie holes. In the method for manufacturing a multilayer printed wiring board, the steps of forming a photopolymer film and forming a multilayer wiring pattern are formed by sequentially repeating the following steps of forming a photopolymer film.
10 mol% of the structural unit represented by the following general formula (I a)
A photosensitive resin composition in which about 3 to 50% by weight of aromatic polyamide having the above properties is dissolved in an organic solvent is used, and the composition is applied onto a wiring pattern and dried. The present invention provides a method for manufacturing a multilayer printed wiring board characterized by:

(However, in the above formula, R1 and R2 represent a hydrogen atom or a residue of a reactive organic compound, Ar1 represents an aromatic residue, and A
r2 represents an aromatic residue containing a photosensitive group. ) The method for manufacturing a multilayer printed wiring board of the present invention will be described in detail below.

First, the photosensitive resin composition used in the manufacturing method of the present invention will be explained.

The photosensitive material of the photosensitive resin composition used in the present invention contains 10 mol% or more, preferably 20 mol% or more, more preferably 4 mol% or more of the structural unit represented by the general formula (Ia).
The aromatic polyamide having a proportion of 0 mol% or more may be a polyamide having a proportion of 80 to 100 mol% of the structural units represented by the general formula (Ia), In addition, the structural unit represented by the following general formula (I b) is 0 to
90 mol%, especially 0-80 mol%, even 0-60 mol%
It may also be an aromatic polyamide having a ratio of .

(However, in the above formula, R3 and h represent a hydrogen atom or a residue of a reactive organic compound, and Ar3 and Ar4 represent an aromatic residue.) In the general formulas (Ia) and (Ib), Ar1 and A
Examples of the aromatic residue represented by r3 include aromatic residues of aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, 4,4''
-dicarboxy-biphenyl, 4.4°-dicarboxy-diphenylmethane, 4.4°-dicarboxy-
Examples include aromatic dicarboxylic acids such as diphenyl ether and their acid halides. Among these aromatic dicarboxylic acid components, acid halides of the above-mentioned aromatic dicarboxylic acids, particularly acid chlorides, are preferred.

In addition, in the general formula (I a), the aromatic residue containing a photosensitive group represented by Ar2 includes an aromatic residue of an aromatic diamine having a photosensitive group, and the aromatic diamine includes: For example, 3゜5-diaminobenzoic acid ethyl acrylate, 2,4-diaminobenzoic acid ethyl acrylate, 3,5-diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate, 3.5-diaminobenzoic acid glycidyl acrylate ester, 2,4-diaminobenzoic acid glycidyl acrylate ester, 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2
．． 4-diaminobenzoic acid glycidyl methacrylate ester, 3,5-diaminobenzoic acid cinnamic ester, 2.
Benzoic acid esters such as 4-diaminobenzoic acid cinnamic ester; 3,5-diaminohensyl acrylate, 3
Benzyl acrylates such as 5-diaminobenzyl methacrylate, 2,4-diaminohensyl acrylate, 2,4-diaminobenzyl methacrylate-1; 4-
Acrylamide-3,4''-diaminodiphenyl ether, 2-acrylamide-3,4''-diaminodiphenyl ether, 4-cinnamamide-3,4''-diaminodiphenyl ether, 3,4°-diacrylamide-3
゛, 4-diaminodiphenyl ether, 3,4''-dicinnamamide 3゛, 4-diaminodiphenyl ether, 4-methyl-2゛-carboxyethyl methacrylate ester-3,4゛-diaminodiphenyl ether [carboxyethyl methacrylate is CH2=C(CH
3) C00CH2CH200C-], 4-methyl-2”-carboxyethyl acrylic acid ester-3,4
゛-Diaminodiphenyl ether [carboxyethyl acrylic acid ester is CHz=CHCOOC) lzcH2
diphenyl ethers such as 00cm; and 4
, 4'-diaminochalcone, 3.3'-diaminochalcone, 3.4'-diaminochalcone, 3", 4-diaminochalcone, 4'-methyl-3', 4-diaminochalcone, 4"-methoxy-3 Examples include chalcones such as 1, 4-thia-9-minochalcone, and 3-methyl-3,5-diaminochalcone.

In addition, in the general formula (Ib), the aromatic residue represented by Ar4 includes an aromatic residue of an aromatic diamine that does not have a photosensitive group, and the aromatic diamine includes:
For example, paraphenylenediamine, metaphenylenediamine, 2.4-diaminotoluene, 4.4''-diaminodiphenyl ether, 4.4''-diaminodiphenylmethane, 0-toluidine, 1.4-bis(4-aminophenoxy)benzene, Diamines such as 2,2′-bis(4-aminophenoxyphenyl)propane, 0-toluidine sulfone, and 9,9-bis(4-aminophenyl)
-10-anthrone, 1.5-diaminoanthraquinone, 1.4-diaminoanthraquinone, 3.3'-diaminobenzophenone, 4'-N,N-dimethylamino-3
, 5-diaminobenzophenone, 1-dimethylamino-
4-(3,5-diaminobenzoyl)-naphthalene 1
0- Which ketone group-containing diamines can be mentioned. Among these, diamines containing ketone groups are particularly preferred because they can further improve the sensitivity and resolution of polyamides.

Furthermore, in the general formulas (Ia) and (Ib), R
Residues of reactive organic compounds represented by 1, R2, R3, and R4 are organic compounds (reactive organic compounds) that have reactivity with the hydrogen atoms of the amide bonds of polyamide. It is an organic group formed as a result of a substitution reaction, and examples include an acetyl group, an acryloyl group, a methacryloyl group, a cinnamoyl group, and a barazidobenzoyl group. In particular, a photosensitive group such as an acryloyl group, a methacryloyl group, and a cinnamoyl group. Organic groups containing these are preferred because they can further improve the sensitivity and resolution of the polyamide. Examples of reactive organic compounds having these residues include methacrylic acid chloride,
Examples include acrylic acid chloride, cinnamic acid chloride, acetic acid chloride, benzyl chloride, and benzoyl balaazide chloride.

In addition, in the polyamide used in the present invention, the presence of the general formula (Ib) has the effect of improving the thermal properties of the polyamide, but if it is too large, the concentration of photosensitive groups decreases and the photosensitivity decreases, so it is necessary to isn't it.

Further, the aromatic polyamide has 0.5 g of polyamide/
The logarithmic viscosity measured at 30°C as a solution with a concentration of 100 ml of N-methyl-2-pyrrolidone is 0.1 to 3.5.
Particularly preferred is one within the range of 0.2 to 2.0.

The polyamide can be manufactured as follows.

That is, in the above polyamide, when R1, R2, R3 and R4 are hydrogen atoms, the above Arl (or Ar
3) and an aromatic diamine 10 having a photosensitive group represented by the following general formula (II).
0 to 10 mol%, preferably 100 to 20 mol%, more preferably 100 to 40 mol%, and the following general formula (II
Aromatic diamines 0 to 9 having no photosensitive group represented by I)
A polycondensate or a copolycondensate (aromatic polyamide) is obtained by polycondensation or copolycondensation with an aromatic diamine component consisting of 0 mol%, preferably 0 to 80 mol%, more preferably 0 to 60 mol%. Obtained by synthesis.

112N-^r2-NR2(II) (However, in the formula, Ar2 represents an aromatic residue containing a photosensitive group.) R2N-Ar4-N R2(II) (However, in the formula, Ar4 represents a photosensitive group. The above synthetic reaction is preferably carried out in an organic solvent at a reaction temperature of 100°C or lower, preferably 80°C or lower for 0.1 to 48 hours.

As the organic solvent in the above polymerization reaction, for example, N, N
-dimethylsulfoxide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, etc. used.

Further, in the aromatic polyamide, R1, R2゜R
When at least one of 3 and - is a residue of a reactive organic compound, R1゜R2,R3 synthesized as described above
The above polycondensate or copolycondensate (aromatic polyamide) in which and - are hydrogen atoms is added to a reactive organic compound having an organic group corresponding to R1, R2, R3 and R4 in the synthesis reaction solution. It is obtained by adding a compound and reacting at a reaction temperature of =5 to 100°C for 0.1 to 48 hours.

Note that among the aromatic diamines represented by the general formula (n) used in the production of the aromatic polyamide, diaminodiphenyl ethers, diaminobenzoic acid esters, and diaminobenzyl acrylates are new compounds, and their synthesis is difficult. Preferred synthesis methods include the following, although the method is not limited.

(11 Synthesis method of diaminodiphenyl ethers) React the (mono- or di)amino-dinitrophenyl ether obtained by hydrolyzing (mono- or di)acetylamide dinitrophe 14-nyl ether with acrylic acid chloride, etc. Then, the target aromatic diamine compound can be synthesized by reducing the reactants.

(2) Synthesis method of diaminobenzoic acid esters One example is a method of synthesizing the desired aromatic diamine compound by reacting dinitrobenzoic acid chloride with hydroxyethyl methacrylate, etc., and then reducing the reactant. .

(3) Synthesis method of diaminobenzyl acrylates An example of this method is to react dinitrobenzyl alcohol with acrylic acid chloride, and then reduce the reactant to synthesize the desired aromatic diamine compound.

Furthermore, among the aromatic diamines represented by the general formula (III) used in the production of the aromatic polyamide, Ar
A compound in which the aromatic residue represented by 4 is R represents a methyl group or an ethyl group (such as the above-mentioned 4'-N,N-dimethylamino-3,5-diaminobenzophenone) is also a new compound, Although the synthesis method is not limited, a preferable synthesis method is to first react dinitrobenzoyl chloride and aniline to synthesize dinitrobenzanilide, and then react this with Ar-N and phosphorus oxychloride. The desired diamine compound can be synthesized by adding concentrated hydrochloric acid to the resulting reaction product and then reducing it.

Further, as the organic solvent constituting the photosensitive resin composition used in the present invention, N,N-dimethylformamide, N
, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,3-dimethyl-2-
Examples include imidaridinone, hexamethylphosphorite triamide, hexamethylenephosphoamide, and the like. This photosensitive resin composition is a solution composition in which the aromatic polyamide is uniformly dissolved in an organic solvent at a ratio of about 3 to 50% by weight, preferably 5 to 40% by weight.

The photosensitive resin composition used in the present invention may contain a thermal polymerization inhibitor, if necessary. Examples of such thermal polymerization inhibitors include hydroquinone, 2,6-di-t-butyl-4-methylphenol (BHT), methyl ether hydroquinone, and benzoquinone.

The appropriate amount of the thermal polymerization inhibitor is about 0 to 3 parts by weight per 100 parts by weight of the polyamide.

Furthermore, a sensitizer and a photopolymerization initiator can be added to the photosensitive resin composition used in the present invention, if necessary. Such sensitizers and photopolymerization initiators include Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-benzo-9°10-anthraquinone, 4,4
-bis(diethylamino)benzophenone, acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or its derivatives (e.g. chlorothioxanthone, methylthioxanthone), anthranilic acid dimethylaminobenzoate, etc., which may be used alone or A mixture of two or more types is used. The blending amount of this sensitizer and photopolymerization initiator is as follows:
Approximately 1 to 10 parts by weight is appropriate.

The photosensitive resin composition used in the present invention has a viscosity with a rotational viscosity of about 1 to 5000 poise, particularly 5 to 1000 poise, and more preferably 10 to 500 poise, measured at room temperature.
The polyamide solution composition is preferably colorless and transparent.

18- Next, an outline of one embodiment of the method for manufacturing a multilayer printed wiring board of the present invention using the above-mentioned photosensitive resin composition will be explained with reference to the drawings.

A typical embodiment of the present invention has the following four steps as basic steps.

Step i) Formation of first layer wiring pattern On the insulating substrate,
The first layer wiring pattern 2 is formed by an additive process or a photoetching process. This step is usually carried out in a conventional manner using a conventional photosensitive resin on a copper-clad insulating substrate.

Step ii) Forming a photopolymer film On the first layer wiring pattern 2 obtained in step ii),
The photosensitive resin composition of the present invention described above has a thickness of about 5 to 2000 μm.
, preferably 10 to 1000 tlm, more preferably 30 to 800 μm, and dried to form a photopolymer film 3 with an average thickness of about 2 to 200 μm, preferably 5 to 150 μm. do. This photopolymer II! By forming the film 1ti3, the first layer wiring pattern 2 is covered and buried with the film 3.

Step iii) Formation of a photocured film having hole holes The photopolymer film 3 obtained in step ii) is covered with a predetermined positive mask, exposed to ultraviolet light, etc., and N-methyl-2
- The uncured portion is washed off using a solvent such as pyrrolidone, developed, and washed with water to form a photocured film with piere balls 4 formed at predetermined positions that are electrically connected to the first layer wiring pattern. This photocured film forms the glabellar insulating film 3'.

Step iv) Step iii of forming the second layer wiring pattern
) A second layer wiring pattern 5 is formed on the glabellar insulating film 3' and on the pie ball 4. A semi-additive method is applied to form the second layer wiring pattern 5. That is, first, electroless copper plating is applied to the interlayer insulating film 3 and the 4 portions of the via hole after surface treatment, and then a second layer is formed using a photosensitive resin for forming a normal wiring pattern. After forming a wiring pattern forming area and electroplating copper on the forming area, the cured film of the photosensitive resin is peeled off, and the electroless copper plating area other than the copper electroplating area is etched, and the electroplating process is performed. A second layer wiring pattern 5 made of copper is formed.

After completing the above steps i) to iv), further steps ii) to i
A desired multilayer printed wiring board is manufactured by repeating step v) as many times as necessary.

The coating and drying of the photosensitive resin composition, and the exposure and development of the photopolymer film in the above steps ii) and iii) are performed as follows.

The photosensitive resin composition can be applied to the substrate using, for example, a rotary coating machine. The coating film is dried at a temperature of 150°C or lower, preferably 100°C or lower.

At this time, the pressure may or may not be reduced. After drying, a negative photomask chart is placed on the coated film, and active light such as ultraviolet rays, visible light, electron beams, and X-rays is irradiated. The unexposed areas are then washed away with a developer to obtain a polyamide relief pattern 21-. The above developer may be a solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, diglyme, or a combination of the solvent and methanol or ethanol. Mixed systems can be used.

The photosensitive material of the photosensitive resin composition used in the method for producing a multilayer printed wiring board of the present invention, that is, the aromatic polyamide, has a photosensitive group introduced into the polymer chain, and is soluble in an organic solvent. Because of its excellent properties, wiring patterns can be easily formed by photochemical means by dissolving it in an organic solvent and using it as a photosensitive resin composition. Because it has excellent light transmittance and photocrosslinkability, it can be easily photocured into a fairly thick film in a short time, and any photocured film can be placed in the desired position, which is impossible with conventional photosensitive materials. It is now possible to easily form a diameter hole of about 300 μm, which was previously possible, and there is no particular need for another photocurable material for image formation, such as conventional non-photosensitive polyimide or polyimide. I don't. In addition, unlike photosensitive polyamic acid (polyimide precursor) and polyamide aminic acid, it does not require an imidization process after image formation, which not only simplifies the process, but also reduces distortion due to thermal effects and shrinkage on the element. It has many excellent effects such as not giving stress.

Moreover, the glabellar insulating film of the photocured film formed using the aromatic polyamide has excellent heat resistance, mechanical properties, and electrical properties, and has good adhesion to the substrate. Since it has excellent light transmittance and photocrosslinkability, it is possible to suitably form a thick film with a thickness of about 30 to 80 μm.

The photosensitive material of the photosensitive resin composition used in the method for producing a multilayer printed wiring board of the present invention has various properties as described above, and can form an insulating film having via holes directly on the wiring pattern. According to the present invention using such a photosensitive material, it is possible to manufacture a multilayer printed wiring board.

As mentioned above, the present invention uses organic solvent-soluble polyamide, which has excellent heat resistance, high sensitivity and resolution, and excellent adhesion to substrates, as a photopolymer, thereby reducing the diameter of the pie hole. This makes it possible to manufacture multilayer printed wiring boards in which the interlayer insulating film, which requires This will greatly contribute to the

Examples of the synthesis of the diamine component used in the production of the polyamide used in the present invention, production examples of the polyamide used in the present invention, and examples of the present invention are shown below.

Synthesis Example 1 First Step 29.6 g of 2-hydroxyethyl methacrylate and 18.1 g of pyridine were dissolved in THF (tetrahydrofuran).
A solution prepared by dissolving 50 g of 3.5-dinitrobenzoic acid chloride in 150 ml of THF was added dropwise from a dropping funnel at 5 to 6° C. over 1 hour to the 200 ml solution. After the dropwise addition, the mixture was further stirred at 10 to 15°C for 1 hour. Thereafter, the precipitated pyridine hydrochloride was filtered out using a Buchner funnel, the filtrate was concentrated, and then poured into water to precipitate a white-yellow precipitate.

The obtained precipitate was washed several times by decantation and then dried in vacuo to obtain 60 g of 3,5-dinitrobenzoic acid ethyl methacrylate.

Second step A solution of 5 g of 3,5-dinitrobenzoic acid ethyl methacrylate obtained in the first step dissolved in 36 ml of acetic acid was added to a solution of 27 g of iron powder suspended in 15 ml of water/35 ml of acetic acid at a reaction temperature of The mixture was added in 2-4 ml portions while stirring to maintain the temperature at 25°C±3°C. The addition was completed in about 20 minutes, and the mixture was stirred for an additional 10 minutes.

Then, using a Buchner funnel, add ice to the filtrate from which excess iron was separated and bring the temperature to about 0°C, and then purge with aqueous ammonia.
After setting t+ to around 8, extraction was performed using ethyl acetate, washing with water and drying, and ethyl acetate was removed to obtain 11.2 g (yield: 67.5%) of the crude target product. This crude target product was purified by column chromatography. That is, 200 g of Wako Gel (c-200) was packed into a 65 mmφ column and separated using a 1:1 mixed solvent of ethyl acetate and benzene as a developing solvent to obtain 7.8 g of the target product.

Melting point 88-89°C Elemental analysis value (as CnlL&Nz 04) HN Actual value (%) 59.36 6.0B 10.49 Calculated value (%) 59. '08 6.10], 0.60 Also, regarding the above target object, infrared absorption spectrum and H-N M
The R spectrum was measured and it was confirmed that it was the desired product.

Production Example 1 ■ Production of Polyamide After purging the inside of the flask with dry nitrogen, 3 g of lithium chloride and 31.71 g of 3,5-diaminobenzoic acid ethyl methacrylate obtained in Synthesis Example 1 were added.
4g of N-methyl-2-pyrrolidone (NM
P) 240 ml was added and melted. After dissolving, cool to 3°C and add terephthalic acid dichloride 24.364 while stirring.
g was added. At this time, heat generation occurred and the temperature of the solution rose to 34°C. This was stirred in ice water for 30 minutes, and then stirred and reacted at room temperature for 1 hour.

Next, 300 ml of NMP was added to the reaction solution to dilute it, and then this was added to a mixed solution of 61 parts of methanol and 61 parts of water to precipitate polyamide. The precipitate was collected by filtration and dried to obtain 42.01 g of white polyamide powder.

Logarithmic viscosity of this polyamide (0.5 g of polyamide /
NMP (100 ml concentration of polyamide solution, 30°C) is 1
．． It was 73.

■ Preparation of photosensitive resin composition To 30 g of the polyamide powder obtained in the above (■), 150 g of NMP as an organic solvent, 1.2 g of Michler's ketone as a photopolymerization initiator, and 0.15 g of hydroquinone and 0 methyl ether hydroquinone as thermal polymerization inhibitors were added. .15
After stirring well to obtain a uniform viscous liquid, fine dust and the like were removed by pressure filtration to prepare a 150 poise photosensitive resin composition.

■Preparation of cured film and measurement results of various characteristic values 7 on copper plate
A spacer with a thickness of 00 μm was provided, and the photosensitive resin composition prepared in step (1) above was poured into it and coated using a bar coater to form a thin film with an average thickness of about 700 μm.
The thin film was dried in a hot air dryer at 70° C. for 2 hours to obtain a film with a thickness of 75 μm. This film was photocured by IJ/c+J irradiation using an ultra-high pressure mercury lamp, and then
Heat treatment was performed at ℃ for 30 minutes to create a cured film.

The results of measuring various characteristic values of this cured film are shown in Table 1 below.

Table 1 29- (Continuation of Table 1) 30- In addition, 1 formed from a commercially available urethane photopolymer
When the above thermal shock test was performed on the cured film having a thickness of 50 μm, cracks were observed in the cured film.

Example 1 Production of 03-layer printed wiring board i) Formation of 1Nth copper wiring pattern Myuron A (
Negative pattern resist (manufactured by Muromachi Kagaku Kogyo@) was laminated, its surface was covered with a 1N-th wiring mask film, and an ultra-high pressure mercury lamp was used to 0.2, J/cta.
After irradiation and exposure of 1.3% sodium carbonate,
It was developed with an aqueous solution of sodium phosphate and washed with water to form a thin film of Myuron A covering the first layer wiring portion.

Next, the substrate was immersed in a 65% ferric chloride aqueous solution to remove unnecessary copper on the substrate by etching, and then etched with an additional 3% ferric chloride solution.
The thin film of Myuron A was peeled off by immersion in an aqueous sodium hydroxide solution to form a first layer copper wiring pattern.

ii) Formation of polyamide' film A 700 μm thick spacer was provided on the substrate obtained in step i) above on which the first layer copper wiring pattern was formed, and a spacer with a thickness of 700 μm was provided on this. The resulting photosensitive resin composition was applied to form a thin film with an average thickness of about 650 μm,
It was dried at 70°C for 2 hours to form a polyamide film with a thickness of 70 μm.

iii) Formation of hole holes The surface of the polyamide film formed in step ii) above was covered with a mask pattern for through-holes, and exposed to IJ/cnt using an ultra-high pressure mercury lamp.

Via hole development was performed at 28KHz90 in NMP solution.
The cleaning was carried out for 3 minutes using a W ultrasonic cleaner. Furthermore, 5 J
/ cJ irradiation and post-exposure, then 3 cJ at 150°C.
Post-heating was performed for a minute to cure the polyamide film, and the photocured film was left as it was to serve as a glabellar insulating film.

iv) Formation of second layer copper wiring pattern above step iii
) After surface treatment of the glabellar insulating film formed using a scrub cleaner (manufactured by Shipley), electroless copper plating treatment was performed on the interlayer insulating film and the pie hole portion based on Muromachi Chemical Industry's MK series. .

Next, Myuron A was laminated on the electroless copper plating part, the surface was covered with a second layer mask film for wiring, and the film was heated to 0.08 J/cr using an ultra-high pressure mercury lamp.
After irradiation and exposure of a, it was developed with an aqueous solution of 1.3% sodium carbonate and sodium phosphate, and washed with water to form a thin film of Myuron A to obtain a second layer wiring pattern forming part. .

Next, in order to perform electroplating treatment using a copper sulfate bath on the wiring pattern forming portion of the second layer, a copper plate was used as the anode and a substrate was attached to the cathode, based on the Ebara cordierite TH process, under the condition of 2A/dm. , electroplating was performed for 1 hour. Thereafter, the substrate was immersed in a 3% aqueous sodium hydroxide solution to peel off the Myuron A thin film, and further immersed in a 20% ammonium persulfate aqueous solution for several seconds to remove the electroless copper plating formed by electroless copper plating. The unnecessary portions of copper were removed by etching to form a second layer of copper wiring bar 33-turn.

(2) Formation of third layer copper wiring pattern A third layer copper wiring pattern was formed by repeating the above steps 11) to iv).

■Thermal shock test Using the three-layer printed wiring board manufactured in the above ■, MI
A thermal shock test (-65°C, 30 minutes #125°C, 30 minutes, 100 cycles) according to L standard-3TD-202D-107 was conducted to check for the occurrence of cracks and the reliability of continuity, and no abnormalities were found. I was not able to admit.

Production Example 2 ■Production of polyamide After purging the inside of the flask with dry nitrogen, 3 g of lithium chloride and 31.71 g of 3,5-diaminobenzoic acid ethyl methacrylate obtained in Synthesis Example 1 were added.
4g of NMP was added thereto, and 240ml of NMP was added and dissolved.

After dissolving, cool to 2°C and stir once.

Ir' -34-, = ... The temperature rose to 32°C. This was stirred in ice water for 30 minutes, and then stirred and reacted at room temperature for 1 hour.

Thereafter, 300 ml of NMP was added to the reaction solution to dilute it.

Furthermore, methacrylic acid chloride 25, 8 was added to the reaction solution.
A solution prepared by dissolving 50 g of NMP in 30 ml of NMP was added dropwise over 30 minutes. At this time, an exotherm occurred and the temperature of the solution rose to 35°C.

After the reaction, the reaction solution was added to a mixed solution of 6 parts of methanol and 6 parts of water to precipitate polyamide. Filter and dry the precipitate,
51 g of white polyamide powder was obtained. The logarithmic viscosity of this polyamide (polyamide solution with a concentration of 0.5 g of polyamide/100 ml of NMP, 30° C.) was 1.77.

■ Preparation of photosensitive resin composition Using the polyamide powder obtained in the above ■,
A photosensitive resin composition having about 170 voids was prepared in the same manner as above.

Example 2 Using the photosensitive resin composition prepared in Production Example 2,
In the same manner as in Example 1, a three-layer printed wiring board was manufactured and subjected to a thermal shock test to examine the occurrence of cracks and the reliability of continuity, and no abnormality was found.

[Brief explanation of the drawing]

The drawings are schematic diagrams showing the process order of the method for manufacturing a multilayer printed wiring board of the present invention. 1...Insulating substrate 2...First layer wiring pattern 3...Photopolymer film 3''...Interlayer insulating film 4...Pier hole 5...Second layer wiring pattern patent application Jinyubu Kosan Co., Ltd. Engraving of drawings (no change in content) Procedural amendment (method) % formula % 2. Name of invention Method for manufacturing multilayer printed wiring board 3. Relationship with the person making the amendment Patent applicant (020) Ube Industries Co., Ltd. 4, Agent No. 601 Nogizaka, Pacifisoku, 6-29 Akasaka 9-chome, Minato-ku, Tokyo May 29, 1980 (Delivery date) 6. Brief explanation of the drawings of the specification subject to amendment Column and drawing 7, details of amendment (1) "Drawing" in line 8 of page 36 was corrected to "Figure 1." (2) Amend the drawing (no change in content) as attached (
(Amendment to write "Figure 1" on the drawing). that's all

Claims (1)

[Claims] After forming a first layer wiring pattern on an insulating substrate and forming a photopolymer film on the wiring pattern, the photopolymer film is photocured by exposure and developed. Then, a photocured film with pie holes formed therein is formed at a predetermined position, and then, using the photocured film of the photopolymer as an insulating film between the eyebrows, a second film is formed on the glabella insulating film and in the part of the pie holes.
In a method for manufacturing a multilayer printed wiring board, in which a multilayer wiring pattern is formed by forming a wiring pattern for each layer and then sequentially repeating the steps following the photopolymer film formation step described above, the photopolymer film formation is performed by the following general method. Formula (I
Using a photosensitive resin composition in which an aromatic polyamide having 10 mol% or more of the structural unit represented by a) is dissolved in an organic solvent at a ratio of about 3 to 50% by weight, the composition is applied onto a wiring pattern. A method for producing a multilayer printed wiring board, characterized in that it is carried out by coating and drying. (However, in the above formula, R1 and R2 represent a hydrogen atom or a residue of a reactive organic compound, Ar1 represents an aromatic residue,
r2 represents an aromatic residue containing a photosensitive group. )